全文获取类型
收费全文 | 3644篇 |
免费 | 596篇 |
国内免费 | 455篇 |
专业分类
化学 | 2085篇 |
晶体学 | 17篇 |
力学 | 163篇 |
综合类 | 22篇 |
数学 | 311篇 |
物理学 | 1125篇 |
无线电 | 972篇 |
出版年
2024年 | 20篇 |
2023年 | 97篇 |
2022年 | 127篇 |
2021年 | 107篇 |
2020年 | 146篇 |
2019年 | 146篇 |
2018年 | 143篇 |
2017年 | 124篇 |
2016年 | 174篇 |
2015年 | 178篇 |
2014年 | 207篇 |
2013年 | 246篇 |
2012年 | 284篇 |
2011年 | 288篇 |
2010年 | 216篇 |
2009年 | 205篇 |
2008年 | 268篇 |
2007年 | 188篇 |
2006年 | 202篇 |
2005年 | 200篇 |
2004年 | 142篇 |
2003年 | 139篇 |
2002年 | 134篇 |
2001年 | 105篇 |
2000年 | 78篇 |
1999年 | 88篇 |
1998年 | 64篇 |
1997年 | 45篇 |
1996年 | 47篇 |
1995年 | 47篇 |
1994年 | 45篇 |
1993年 | 40篇 |
1992年 | 30篇 |
1991年 | 27篇 |
1990年 | 23篇 |
1989年 | 16篇 |
1988年 | 13篇 |
1987年 | 13篇 |
1986年 | 10篇 |
1985年 | 7篇 |
1984年 | 8篇 |
1983年 | 3篇 |
1982年 | 1篇 |
1981年 | 3篇 |
1936年 | 1篇 |
排序方式: 共有4695条查询结果,搜索用时 15 毫秒
61.
Zhan W Jiang Y Sharma S Brodie PJ Bane S Kingston DG Liotta DC Snyder JP 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(52):14792-14804
A series of conformationally restrained epothilone analogues with a short bridge between the methyl groups at C6 and C8 was designed to mimic the binding pose assigned to our recently reported EpoA-microtubule binding model. A versatile synthetic route to these bridged epothilone analogues has been successfully devised and implemented. Biological evaluation of the compounds against A2780 human ovarian cancer and PC3 prostate cancer cell lines suggested that the introduction of a bridge between C6-C8 reduced potency by 25-1000 fold in comparison with natural epothilone D. Tubulin assembly measurements indicate these bridged epothilone analogues to be mildly active, but without significant microtubule stabilization capacity. Molecular mechanics and DFT energy evaluations suggest the mild activity of the bridged epo-analogues may be due to internal conformational strain. 相似文献
62.
Zhan Wang Sheng-Yi Liu Jun-Yan Huang Jiu-Hong Yu Yuan-Di Zhao Hong Chen 《Talanta》2010,80(3):1277-3206
Salicylic acid (SA) is a biological substance that acts as a phytohormone and plays an important role in signal transduction in plants. It is important to accurately and sensitively detect SA levels. A gold electrode modified with copper nanoparticles was used to assay the electrocatalytic oxidation of salicylic acid. It was found that the electrochemical behavior of salicylic acid was greatly improved at copper nanoparticles, indicating that anodic oxidation could be catalyzed at copper nanoparticles. And the pH had remarkable effect on the electrochemical process, a very well-defined oxidation peak appeared at pH 13.3 (0.2 M NaOH). The kinetics parameters of this process were calculated and the heterogeneous electron transfer rate constant (k) was determined to be 1.34 × 10−3 cm s−1, and (1 − α)nα was 1.22. The gold electrode modified with copper nanoparticles could detect SA at a higher sensitivity than common electrodes. The electrode was used to detect the SA levels in oilseed rape infected with the fungal pathogen Sclerotinia sclerotiorum. The results showed that the SA concentration reached a maximum during the 10th-25th hours after infection. This result was very similar to that determined by HPLC, indicating that the gold electrodes modified with copper nanoparticles could be used as salicylic acid sensors. 相似文献
63.
Yan Zhan Yang Wang Qunfeng Cheng Chang Li Kaixuan Li Huizeng Li Jingsong Peng Bo Lu Yu Wang Yanlin Song Lei Jiang Mingzhu Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(46):16608-16614
Extensive applications for photodetectors have led to demand for high‐responsivity polarization‐sensitive light detection. Inspired by the elaborate architecture of butterfly Papilio paris, a 1D nanograting bonded porous 2D photonic crystal perovskite photodetector (G‐PC‐PD) using a commercial DVD master and 2D crystalline colloidal arrays template was fabricated. The coupling effect from grating diffraction and reflection of the PC stopband renders the enhanced light harvesting of G‐PC‐PD. The porous scaffold and nanoimprinting process afford a highly crystalline perovskite film. White light responsivity and detectivity of G‐PC‐PD are up to 12.67 A W?1 and 3.22×1013 Jones (6~7 times that of a pristine perovskite photodetector). The highly ordered nanograting arrays of G‐PC‐PD enable polarization‐sensitive light detection with a rate of ?0.72 nA deg?1. This hierarchical perovskite integrated nanograting and 2D PC architecture opens a new avenue to high‐performance optoelectronic devices. 相似文献
64.
Storage stabilities of LiFePO4/C composite at different conditions are investigated in terms of structural and electrochemical evolutions. The results from different aging tests indicate that moisture and temperature are the key factors that have the most profound effects on the structure homogeneity which in turn influences the electrochemical performance of LiFePO4/C. Although the storage in a humid‐hot environment, such as saturated humidity air at 50°C, does not greatly influence the discharging capacity of LiFePO4/C, it does reduce the initial charging capacity, thus the amount of reversible Li+ ions in a practical LiFePO4/graphite cell decreases. This impact is explained by the lithium extraction during the storage, forming olivine FePO4 and associated Li3PO4. Elevated storage temperature also favors the delithiation process. The degree of delithiation increases from about 6% at 50°C to 18% at 80°C. It is also found that re‐calcination at 650°C effectively resolves the problem of the structural heterogeneity of the stored LiFePO4/C. Therefore both the initial charging capacity and coulombic efficiency of the stored sample in the first cycle revert to the original value of the fresh one. 相似文献
65.
Enhanced Electrochemical Performances of LiFePO4/C via V and F Co-doping for Lithium-Ion Batteries 下载免费PDF全文
Based on the method of in situ polymerization synthesis combined with two-step sinter-ing process, LiFe1-xVx(PO4)(3-y)/3Fy/C was prepared. The e ects of V and F co-doping on the structure, morphology, and electrochemical performances of LiFePO4/C were in-vestigated by X-ray di raction, Fourier transform infrared spectra, scanning electron mi-croscope, charge/discharge tests, and electrochemical impedance spectroscopy, respectively. The results indicated that the V and F co-doping did not destroy the olivine structure of LiFePO4/C, but it can stabilize the crystal structure, decrease charge transfer resistance, enhance Li ion di usion velocity, further improve its cycling and high-rate capabilities of LiFePO4/C. 相似文献
66.
Zhan Yu Lee Chuin Chen Rosa Erra‐Balsells Hiroshi Nonami Kenzo Hiraoka 《Rapid communications in mass spectrometry : RCM》2010,24(11):1507-1513
Probe electrospray ionization (PESI) is a modified version of the electrospray ionization (ESI), where the capillary for sampling and spraying is replaced by a solid needle. High tolerance to salts and direct ambient sampling are major advantages of PESI compared with conventional ESI. In this study, PESI‐MS was used to monitor some biological and chemical reactions in real‐time, such as acid‐induced protein denaturation, hydrogen/deuterium exchange (HDX) of peptides, and Schiff base formation. By using PESI‐MS, time‐resolved mass spectra and ion chromatograms can be obtained reproducibly. Real‐time PESI‐MS monitoring can give direct and detailed information on each chemical species taking part in reactions, and this is valuable for a better understanding of the whole reaction process and for the optimization of reaction parameters. PESI‐MS can be considered as a potential tool for real‐time reaction monitoring due to its simplicity in instrumental setup, direct sampling with minimum sample preparation and low sample consumption. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
67.
采用简单高温煅烧法成功制备了磁性钴镍基氮掺杂三维碳纳米管与石墨烯复合材料(CoNi@NGC),将其作为吸附剂用于水体中6种双酚类化合物(BPs)的吸附性能和机理研究。将CoNi@NGC复合纳米材料用作萃取介质,运用酸碱泡腾片的CO2强力分散作用,开发了泡腾反应强化的分散固相微萃取前处理方法,结合高效液相色谱-荧光检测(HPLC-FLD)快速定量饮料中痕量BPs。采用扫描电镜、透射电镜、傅里叶红外光谱、氮气吸脱附、X射线光电子能谱和磁滞回线等技术手段对材料形貌结构进行表征,结果显示:该吸附剂成功实现氮元素的掺杂,且具有较大的比表面积(109.42 m2/g)、丰富的孔径及较强的磁性(17.98 emu/g)。吸附剂投加量、pH、温度、时间等因子优化试验表明:当pH=7,在初始质量浓度为5 mg/L的BPs混合溶液中投加5 mg CoNi@NGC, 298 K反应5 min,对双酚M(BPM)、双酚A(BPA)的吸附率分别高达99.01%和98.21%。作用90 min时对双酚Z(BPZ)、BPA、BPM的吸附率近100%。在吸附过程中,BPs与CoNi@NGC之间的整个吸附过程主要受氢键、静电作用和π-π共轭作用共同控制。整个吸附过程符合Freundlich吸附等温线模型和准二级动力学方程,吸附自发进行。进一步将CoNi@NGC作为萃取介质制备成磁性泡腾片,利用泡腾分散微萃取技术高效富集和提取6种盒装饮料中的BPs,优化了影响富集效果的泡腾片的存在与否、洗脱剂种类、洗脱时间、洗脱体积等关键因子,在最佳萃取条件下(pH=7,投加5 mg CoNi@NGC, 2 mL丙酮洗脱6 min),结合HPLC-FLD,新开发的泡腾分散微萃取方法提供的检出限为0.06~0.20 μg/L,定量限为0.20~0.66 μg/L,日内和日间精密度分别为1.44%~4.76%和1.69%~5.36%,在实际样品中不同水平下的加标回收率为82.4%~103.7%,在桃汁中检测到BPA和双酚B(BPB)分别为2.09 μg/L和1.37 μg/L。再生试验表明该吸附材料至少可以重复使用5次以上,显著降低了分析的试验成本。与其他方法相比,该方法具有灵敏度高、萃取速度快、环境友好等优点,在常规食品污染监测中具有较强的应用价值。 相似文献
68.
纤维素是木质纤维素生物质中最为丰富的组分,将其催化转化制备高附加值化学品在生物质资源化利用中占据极为重要的一席之地。由于纤维素中氧含量过高,需选择性地脱除部分氧原子才可获得满足当前化学工业对各类高值化学品的要求。近年来,针对纤维素以及由其衍生的关键平台分子葡萄糖和5-羟甲基糠醛(HMF)等催化脱氧的研究已引起广泛关注,并取得诸多重要进展。在此,我们总结了具有代表性的多相催化剂体系,讨论了利用氢解或脱水脱氧策略分别将纤维素和葡萄糖等分子中一个或多个C―O键裁剪制备乙醇、烯烃或己二酸等的研究。我们还着重介绍了HMF和其衍生的呋喃化合物选择性剪切C―OH/C=O键或呋喃环中的C―O―C键分别制备二甲基呋喃和1, 6-己二醇等催化体系。此外,对各多相催化剂的作用机制和特定C―O断键机理也分别进行了探讨,以期深入理解纤维素及其衍生物的催化脱氧反应。 相似文献
69.
Chinese Journal of Polymer Science - We synthesize and compare four near-infrared absorbing fused-ring electron acceptors named as nTTIC (n=2, 3, 4, and 5), based on different number of... 相似文献
70.
Changmao Wang Yaqin Wang Haitang Xie Cuijiao Zhan Xuejun He Ran Liu Rongfeng Hu Jie Shen Yuanwei Jia 《Biomedical chromatography : BMC》2022,36(3):e5287
In this work, we developed and validated a highly sensitive, rapid and stable LC–MS/MS method for the determination of ibuprofen in human plasma with ibuprofen-d3 as a stable isotopically labeled internal standard (SIL-IS). Human plasma samples were prepared by one-step protein precipitation. The chromatographic separation was achieved on a Poroshell 120 EC-C18 (2.1 × 50 mm, 2.7 μm). Aqueous solution (containing 0.05% acetic acid and 5 mm NH4Ac) and methanol were selected as the mobile phase with gradient elution. An electrospray ionization source was applied and operated in negative ion mode. Multiple reaction monitoring mode was used for quantification using target fragment ions m/z 205.0 → 161.1 for ibuprofen and m/z 208.0 → 164.0 for SIL-IS, respectively. This method exhibited a linear range of 0.05–36 μg/ml for ibuprofen with correlation coefficient >0.99. Mean recoveries of ibuprofen in human plasma ranged from 78.4 to 80.9%. The RSD of intra- and inter-day precision were both < 5%. The accuracy was between 88.2 and 103.67%. The matrix effect was negligible in human plasma, including lipidemia and hemolytic plasma. A simple, efficient and accurate LC–MS/MS method was successfully established and applied to a pharmacokinetic study in healthy Chinese volunteers after a single oral administration of ibuprofen granules. 相似文献